Method of preparing synthetic lubricating oil



United States Patent Jerse No ran/lug. Filed Dec. 3, 1962, Ser. No. 241,517 9 Claims. (Cl; 260-68315) This invention relates to the preparation of synthetic lubricating oils having unusually high viscosity indexes and low pour points by the polymerization of certain straight chain alpha olefins by means of a particular type of catalyst system.

The are various special applications for lubricating oils in which it is highly desirable that the oil employed have an especially high viscosity index, for example, a V.I. above 130. The oil also should have a low pour point, e.g., below -30 F., high oxidation stability andlubricating properties that provide good wear characteristics. One such application is in the lubrication of jet aircraft wherein conditions of both low and high temperature may be encountered. Other special applications in which lubricants having such characteristics are desirable are automatic transmission lubrication, high temperature hydraulic applications and brake fluids. Lubricating oils that can be derived from petroleum generally do not have the combination of properties desired for these special applications.

Lubricating oils having viscosity indexes considerably higher than for those normally derived from petroleum have been prepared heretofore by the polymerization of various olefins. In the prior art several catalyst systems have been disclosed for eiiecting this reaction to produce oily polymers. Aluminum chloride is one of the catalysts that has been used for this purpose (Montgomery et al. United States Patent No. 2,559,984). This catalyst promotes reaction by a cationic type of mechanism, and accordingly it not only efiects polymerization of the olefin but also causes isomerization of both the olefin monomer before polymerization and the polymerization product. This is disadvantageous, since the polymer products obtained in systems where isomerization occurs have lower viscosity indexes than would result in the absence of isomerization.

Garwood United States Patent No. 2,937,129 discloses the use of another type of catalyst system r'or producing polymeric lubricating oils, namely, ditertiary alkyl peroxides. This type ofcatalyst promotes reactions by a free radical mechanism and it also has the disadvantage of causing isomerization as well as polymerization to occur.

The polymerization of ethylene to oils by utilizing a combination of TiCL; and an aluminum alkyl halide such as aluminum ethyl sesquichloride has been described in White et al. United States Patent No. 2,993,942. This type of catalyst system contains both anionic and cationic components, and with higher olefins it also will cause isomerization of the olefin monomer and polymer product to occur. With ethylene a the starting olefin, isomerization of the monomer of course cannot take place but the polymer product has such a high pour point that it generally is not a suitable lubricant for the special types of applications referred to above.

The present invention is directed to the preparation of synthetic lubricating oils by the polymerization of alpha olefins utilizing a catalyst system which promotes reaction mainly by an anionic mechanism so that isomerization reactions are minimized. The starting olefin can be any straight chain alpha olefin of the c 41 range or mixtures thereof. The total oil product boiling above 650 F. that is produced by the reaction generally has a viscosity index above and a pour point substantially below -50 F. The product, after hydrogenation to saturate double bonds in the polymer, has excellent oxidation stability and provides good Wear characteristics in lubricating applications.

According to the invention, synthetic lubricating oils are prepared by contacting one or more alpha olefins of the (2 43 range in a liquid reaction medium or solvent at a temperature in the range of 0-50 C. with a catalyst system formed from the following three types of components:

(1) Aluminum alkyl sesquichloride. (2) Titanium tetrachloride (3) A tetraalkyl silicate The tetraalkyl silicate component of the catalyst sys tem is one in which the alkyl groups each have l-4 carbon atoms and are unbranched. In other words the alkyl groups can be methyl, ethyl, n-propyl or n-butyl. The four alkyl groups can allbe the same or the silicate can contain mixed alkyl groups of the class specified. Thus examples of the silicate component are tetramethyl silicate, tetraethyl silicate, tetra n-butyl silicate, methyl triethyl silicate, diethyl' dipropyl silicate and methyl diethyl butyl silicate.

The aluminum-containing component of the catalyst system must be a sesquichloride, as the desired results cannot be obtained with either an aluminum dialkyl monochloride or an aluminum alkyl dichloride. The alkyl group in the sesquichloride can contain, for example, from one to ten carbon atoms and preferably is a straight chain alkyl group. The sesquichloride can contain branched chain alkyl groups such as isobutyl or isopentyl, although this is not preferred. Examples of suitable alkyl groups in the sesquichloride are methyl, ethyl, propyl, n-butyl, n-hexyl, n-octyl and n-decyl.

It is highly important for obtaining the best products in good yield that the three components of the catalyst system be present in certain proportions. In the first place the aluminum alkyl sesquichloride and the titanium tetrachloride should be used in amounts such that the atomic ratio of A1 to Ti is in the range of 0.82.5 and more preferably 1.0-1.6. At Al:Ti ratios below 0.8, the desired vescosity-ternperature characteristics of the product cannot be secured, while at ratios above 2.5 the viscositytemperature characteristics for the oils are poorer and also there is a tendency to produce solid polymers. Secondly, it is highly important that the amount of tetraalkyl silicate employed in the catalyst system be such that the atomic ratio of O to Al is within a certain narrow range. This range is 0.4:1 to 08:1, and the most preferred range. is 0.5-0.7. Reduction of the O. to Al ratio below 0.4 results in poorer viscosity-temperature characteristics for the product, While an increase of the ratio above 0.8 causes a low yield of product. The most preferable O to Al ratio is about 0.67, as it gives excellent viscosity-temperature characteristics with substantially a maximum yield of product.

The reaction is carried out utilizing a solvent which can be a saturated hydrocarbon or certain types of halohydrocarbons. When a saturated hydrocarbon is used, it can be a paratfinic hydrocarbon, including both nparailins and isoparaflins, or a naphthenic hydrocarbon or mixtures thereof. Examples of suitable hydrocarbon solvents are n-pentane, isopentane, hexanes, octanes, decanes, cyclohexane, methylcyclopentane, dimethylcyclohexane and the like. An aromatic hydrocarbon, such as benzene or toluene, should not be used since it causes the formation: of too much dimer which boils below the lubricating oil range desired. Also with an aromatic hydrocarbon solvent, there-is a tendency to obtain alkylation of the aromatic if even small amounts of water happen to be present in the system.

The types of halohydrocarbons that are suitable as the reaction medium are halobenzenes having 12 halogen varied. The silicate used was tetraethyl silicate, the solvent was dried n-hexane and the monomer employed was substantially pure octene-l. A stirred reactor which had been carefully dried was employed. The reaction mixatoms, trihaolethanes, tetrahaloethanes, trihaloethylenes 5 tures were prepared by adding to the reactor, in the and tetrahaloethylenes, in which halohydrocarbons the order named, n-hexane, ethyl aluminum se'squichloride, halogen can be eitherchlorine or fluorine or both. Par- TiCl tetraethyl silicate (except in Run 1) and octene-l. ticularly. suitable solvents are the monohalobenzenes, viz. The aluminum, titanium and silicon compounds were chlorobenzene and fluorobenzene, and dihalobenzenes each added as a solution in n-hexane. The total amount which are liquid at the reaction temperature such as of n-hexane was 65 ml., the TiCl amounted to 2.77 g. orthoand meta-dichlorobenzenes or difiuorobenzenes, and the amount of octene-l used was 280 g. In each run since with such solvents considerably higher yields of the atomic ratio of Al to Ti was 1.25. The atomic ratios polymer lubricating oil per gram of T iCl used are genof O to Al inthe runs varied from zero in Run I to 6.8 erally obtainable than when a saturated hydrocarbon in Run IV. All runs were carried out at a temperature reaction medium is employed. Examples of other haloof about 15C. for. a time of hours. The catalyst hydrocarbons that can be used are: methyl chlorowas then deactivated by adding to the reaction mixture form; 1,1,2 trichloroethane; 1,1,2,2 tetrachloroethane; 20 g. of Na C0 adding ml. of water with thorough trifluoroethanes; chlorodilluoroethanes; tetrafiuoroethane; mixing and then filtering. The filtrate was topped to and similar ethylene derivatives containing 34 halogen remove solvent and unreacted octene. The polymer was atoms which are chlorine and/or fluorine. The solvent 20 .then distilled under vacuum, to remove the dimer and can be used in an amount such that the weight ratio of obtain the lubricating oil polymer as residuum. Results olefin monomer to solvent is in the range of 5:95 to including viscosity and pour point characteristics of the :5 and more preferably 1:2 to 4:1. lubricating oil products are shown in the accompanying The weight proportion of olefin charge to titanium table. tetrachloride used in the reaction mixture can vary wide- 25 EXAMPLES V JI i a hydrocarbfin siallvfint 1S fimployed Two comparative runs were made to show the effect thls.ratlo shquld be the to 1001 the of incorporating tetraethyl silicate in the catalyst when Opnmum welgkft f generally 15 a l range of to the solvent is chlorobenzene. In each of these runs the 75 a who about Girdle monomer reaction mixture contained 181 ml. of chlorobenzene, 300 typically is converted to polymer berore tne catalyst be- 30 of octengl 10 g. of Tick and an amount of ethyl comes deactivated. While at :1 ratio the conversion is aluminum sssquichloride m provide an atomic ratio of about 66% of the monomer. At higher ratios when the 1 to Ti f 1 25 In Run V no silicate was used whim solvfint is a Saturated hydrocarbon Practically more in Run VI tetraethyl silicate was included in the catalyst of t 1110I10mer is Converted than Occurs at 10011- in amount to provide an atomic ratio of O to A1 of 0.5. W halohydrocarbons are used as the Solvent, the Both runs were carried out at 30 C. for 20 hours. The catalyst is generally capable of effecting a greater converreaction product was worked up in the same manner as sion of the olefin monomer and hence a higher proportion before and the results are also shown in the table.

Table Atomic Ratios Higher Polymer Conversion Wt. R Solvent of Octene-l, Percent OzAl AlzTl Wt. Percent Dimer KVioo KVmo V1. Pioi ui 6. 8 1.25 1. O (elastomeric polymer) of the order of 85% are obtainable at ratios up to 209:1,

70% at a 300:1 ratio and 37% at a 400:1 ratio.

The temperature for carrying out the reaction is in the range of O-50 C. With a saturated hydrocarbon solvent a temperature of 1030 C. preferably is used, while with a halohydrocarbon solvent the preferred temperature is 2540 C. The molecular weight of the product tends to increase with increasing reaction temperature. At temperatures below 0 C. substantially no reaction is obtained, while at temperatures above 50 C. the viscosity of the product becomes extremely high and also the catalyst becomes considerably less active.

The following examples are illustrative and show the importance ofincorporating the tetraalkyl silicate in the catalyst system in an amount to provide an atomic ratio of O to Al within the range previously specified.

EXAMPLES LIV 'A series of comparative runs was made in which the reaction conditions were identical except that the amount of tetraalkyl silicate incorporated in the catalyst was From the data in the table it can be seen that oil products having viscosity indexes above were obtained only when the OzAl ratio was within the range previously specified (0.4-0.8). Results from the series of runs made with hexane as solvent show that an increase in the OtAl ratio above the desired range causes conversion of the monomer to drop and the oil product to have a viscosity considerably higher than is desirable for most uses. At high ()zAl ratios the system has practically no catalytic activity and the small amount or product that may be obtained is an elastomeric polymer rather than oil. By operating with ratios of the catalytic components as herein specified, oils having unusually high viscosity indexes and low pour points can be obtained in good yields. These oils after being hydrogenated have good lubricating characteristics and excellent oxidation stability. 5 A comparison of Runs Ill and VI shows that the use of chlorobenzene instead of a saturated hydrocarbon solvent is advantageous in that a considerably higher amount of the desired oil product can be obtained per gram of TiCl used. Thus in Run ii the grams of desired oil per gram of TiCl were 65 as compared to 156 in Run V1. 7

When other tetraalkyl silicates as herein specified are r substituted for tetraethyl silicate, results substantially 1. Method of preparing a synthetic lubricating oil which comprises contacting straight chain alpha olefin of the (Z -C range in a liquid reaction medium selected from the group consisting of saturated hydrocarbons, halobenzenes having 1-2 halogen atoms, trihaloethanes, tetrahaloethanes, trihaloethylenes and tetrahaloethylenes, in which halohydrocarbons the halogen is selected from the group consisting of chlorine and fluorine, at a temperature in the range of -50? C. with a catalyst system formed from an aluminum alkyl sequichloride, titanium tetrachloride and a tetraalkyl silicate in which the alkyl groups each have 1-4 carbon atoms and are unbranched, the amounts of the aluminum alkyl sesquichloride and titanium tetrachloride being such that the atomic ratio of Al to Ti is in the range of 0.82.5 and the amount of said silicate being such that the atomic ratio of O to Al is in the range of 0.4-0.8, and thereafter separating from the reaction mixture olefin polymer of lubricating oil boiling range.

2. Method according to claim 1 wherein the ratio of O to Al is in the range of 0.5-0.7.

3. Method according to claim 2 wherein the Al to Ti is in the range of 1.0-1.6.

4. Method according to claim 1 wherein said silicate is tetraethyl silicate.

5. Method according to claim 1 wherein the reaction medium is a monohalobenzene.

6. Method according to claim 5 wherein said temperature is in the range of 2540 C.

7. Method according to claim 1 wherein said sesquichloride is aluminum ethyl sesquichloride.

8. Method of preparing a synthetic lubricating oil which comprises contacting straight chain alpha olefin of the (J -C range in a liquid reaction medium selected from the group consisting of saturated. hydrocarbons, halo'oenzenes having 12 halogen atoms, trihaloethanes, tetrahaloethanes, trihaloethylenes and tetrahaloethylenes, in which halohydrocarbons the halogen is selected from the group consisting of chlorine and fluorine, at a temperature in the range of 0-50 C. with a catalyst system formed from an aluminum alkyl sesquichloride, titanium tetrachloride and tetraethyl silicate, the amounts of the aluminum alkyl sesquichloride and titanium tetrachloride being such that the atomic ratio of Al to Ti is in the range of 1.0-1.6 and the amount of tetraethyl silicate being such that the atomic ratio of O to Al is in the range of 0.5-0.7, and thereafter separating from the reaction mixture olefin polymer of lubricating oil boiling range. V

9. Method according to claim 8 wherein the reaction medium is chlorobenzene and thetemperature is in the range of 25-40 C.

References Cited by the Examiner UNITED STATES PATENTS 2,827,447 3/58 Nowlin et al. 260-68315 3,108,145 10/63 Antonsen 260-68315 FOREIGN PATENTS 873,067 7/61 Great Britain.

ALPHONSO D. SULLIVAN, Primary Examiner. PAUL M. COUGHLAN, Examiner. 

1. METHOD OF PREPARING A SYNTHETIC LUBRICATING OIL WHICH COMPRISES CONTACTING STRAIGHT CHAIN ALPHA OLEFIN OF THE C6-C14 RANGE IN A LIQUID REACTION MEDIUM SELECTED FROM THE GROUP CONSISTING OF SATURATED HYDROCARBONS, HALOBENZENES HAVING 1-2 HALOGEN ATOMS, TRIHALOETHANES, TETRAHALOETHANES, TRIHALOETHYLENES AND TETRAHALOETHYLENES, IN WHICH HALOHYDROCARBONS THE HALOGEN IS SELECTED FROM THE GROUP CONSISTING OF CHLORINE AND FLUORINE, AT A TEMPERATURE IN THE RANGE OF 0-50*C. WITH A CATALYST SYSTEM FORMED FROM AN ALUMINUM ALKYL SEQUICHLORIDE, TITANIUM TETRACHLORIDE AND A TETRAALKYL SILICATE IN WHICH THE ALKYL GROUPS EACH HAVE 1-4 CARBON ATOMS AND ARE UNBRANCHED, THE AMOUNTS OF THE ALUMINUM ALKYL SESQUICHLORIDE AND TITANIUM TETRACHLORIDE BEING SUCH THAT THE ATOMIC RATIO OF AL TO TI IS IN THE RANGE OF 0.8-2.5 AND THE AMOUNT OF SAID SILICATE BEING SUCH THAT THE ATOMIC RATIO OF O TO AL IS IN THE RANGE OF 0.4-0.8, AND THEREAFTER SEPARATING FROM THE REACTION MIXTURE OLEFIN POLYMER OF LUBRICATING OIL BOILING RANGE. 